The phrase "Third World" originated during the Cold War. The First World was your side in the Cold War, the Second World was the other side, and the Third World was the poor countries that were not involved. So the Second World was the Communist world if you were a Westerner and the Capitalist world if you were an Easterner.

""Second World" refers to the former communist-socialist, industrial states, (formerly the Eastern bloc, the territory and sphere of influence of the Union of Soviet Socialists Republic) today: Russia, Eastern Europe (e.g., Poland) and some of the Turk States (e.g., Kazakhstan) as well as China."
http://www.nationsonline.org/oneworld/third_world_countries.htm

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